NOx removal system for biogas engines at anaerobic digestion facilities

ABSTRACT

Provided herein are methods, devices and systems comprising a reactor that is operatively connected to: (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust.

This application claims the benefit under §119 of U.S. Appl. No. 61/335,072 filed Dec. 31, 2009, which is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

The United States Environmental Protection Agency (EPA)'s mission is to protect human health and the environment. To achieve this mission, EPA implements a variety of programs under the Clean Air Act that focus on reducing outdoor, or ambient, concentrations of air pollutants that cause smog, haze, acid rain, and other problems; reducing emissions of toxic air pollutants that are known to, or are suspected of, causing cancer or other serious health effects; and phasing out production and use of technologies that destroy stratospheric ozone. These pollutants come from stationary sources (like chemical plants, gas stations, and power plants) and mobile sources (like cars, trucks, and planes). State and local governments have also enacted legislation and implemented guidelines to encourage the development of clean technologies.

SUMMARY OF THE INVENTION

Biogas engines pollute the environment by contaminating air with NOx emissions. Accordingly, local, state and federal NOx regulations have established maximum levels of NOx production for biogas engines. For example, the California Energy Commission (CEC) has established guidelines for certification of combined heat and power engine systems, including for example, biogas engines, that limit NOx emission levels pursuant to California's recently enacted Waste, Heat and Carbon Emissions Reduction Act. Similarly, the local San Joaquin Air Board has established Rule 4702 that governs NOx emissions of biogas engines. These stringent NOx emission standards are a hindrance to the operation of biogas engines.

NOx, however, is not the only greenhouse gas. California, as an example, is home to about 1,750 dairies and 1.8 million dairy cows, producing in aggregate about 35-40 million tons of manure each year. Manure management consists primarily of converting the raw manure to a form that is acceptable for spreading on agricultural fields. Typically, flush water from animal holding areas is transferred to settling tanks for removal of large solid particles, and then stored in holding ponds. During the holding period, anaerobic bacteria convert carbohydrates, fatty acids, and other high energy organic compounds to methane and carbon dioxide that is then typically released into the atmosphere. The liquid suspension remaining after this stabilization process has reduced odor, reduced pathogens, and is less attractive to flies and other nuisance species. As a result of these processes, large quantities of the greenhouse gas methane are released into the atmosphere. Methane is approximately 21 times more potent than carbon dioxide in its global warming potential, and its relatively short atmospheric half life of 12 years makes it an excellent candidate for reducing global warming in the short term. Biogas produced by anaerobic digestion of dairy manure is 50-65% methane, with the remainder being carbon dioxide and a variety of trace gases including hydrogen sulfide. Collecting and combusting the biogas mixture in a reciprocating internal combustion engine has a two-fold favorable effect on greenhouse emissions. The methane is converted to an equal quantity of carbon dioxide, a gas with lower greenhouse warming potential, and the production of an approximately equal quantity of carbon dioxide from the burning of fossil fuels is avoided. The methane produced and released into the atmosphere by California dairy manure management processes totals 450,000 tons per year. It is envisioned by the instant inventors that utilizing methane from dairy farms for electricity generation would be equivalent to removing 2 million motor vehicles from operation. There are an estimated 1,000 dairies in California alone that will benefit from the technology described herein.

NOx emissions from combustion of biogas generated by anaerobic digestion facilities are a serious problem that significantly impedes expansion of biogas utilization for electricity generation. Nitrogen oxides are one of six criteria pollutants for which the Clean Air Act requires the EPA to set National Ambient Air Quality Standards (NAAQS). While exposure to high levels of nitrogen oxides has human health effects, their adverse environmental effects are primarily due to secondary reactions in the atmosphere. For example, the photochemical reaction of NO₂ with volatile organic compounds (VOC's) produces ozone, an important air pollutant and lung irritant. Under the Clean Air Act, each state must develop a plan describing how it will meet the NAAQS. Most of the state of California, including the San Joaquin Valley that serves as home to most of the state's dairy farms, fall within a NAAQS ozone non-attainment zone. Distributed generation projects in non-attainment zones are considered “minor sources” subject to emissions standards set by the states. For all new distributed generation facilities coming on line after Jan. 1, 2007, the California Air Resource Board (CARB) has set NOx emissions limits of 0.07 lb/MW hr. The current high cost of reducing NOx emissions has effectively suspended many California manure based anaerobic digestion projects. The fraction of U.S. counties lying within ozone non-attainment zones is expected to increase over coming years as increasingly strict NAAQS come into effect. In fact, it is believed by many in the industry that without an expensive transition metal-based catalytic convertor, the exhaust from the biogas engine contains levels of NOx too high to legally operate.

Internal combustion engines using biogas (or other fuels) produce a mixture of nitrogen oxides including nitric oxide (NO) and nitrogen dioxide (NO2) and other NOx gases via oxidation of atmospheric nitrogen. Conventional reciprocating engines operating without exhaust gas treatment modalities produce approximately 1.4 pounds of NOx per megawatt hour (MW h) which is 20 times the current CARB standard. The benefits to the water and air quality provided by the subject matter described herein are significant.

Provided herein are methods, devices, and systems for the attenuation of NOx emission from biogas combustion utilizing a liquid waste stream and application of principles of extended absorption, wet chemical scrubbing, and/or selective non-catalytic reduction.

In a first aspect, described herein are methods, devices, and systems comprising a reactor that is operatively connected to: (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit.

In a second aspect, provided herein are methods, devices, and systems comprising an engine exhaust that is operatively connected to a reactor and exhaust from the reactor contains an amount equal to or less than about 0.4 grams of NOx per horsepower-hour of energy produced by the engine.

In a third aspect, provided herein are methods, devices, and systems comprising an engine exhaust that is operatively connected to a reactor and exhaust from the reactor contains an amount equal to or less than about 1 pound of NOx per MWh of energy produced by the engine.

In a fourth aspect, described herein are methods, devices, and systems comprising a biogas production unit for converting waste to a biogas stream and an engine that is operatively connected to a reactor and the operable connection between the engine and the reactor contains an injection inlet for the introduction of a reactive chemical agent to contact the engine exhaust prior to entrance of the engine exhaust into the reactor.

In a fifth aspect, provided herein is a reactor that is operatively connected to: (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the engine exhaust is operatively connected to the reactor and exhaust from the reactor contains an amount equal to or less than about 0.4 grams of NOx per horsepower-hour of energy produced by the engine.

In a sixth aspect, provided herein is a reactor that is operatively connected to: (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the engine exhaust is operatively connected to the reactor and exhaust from the reactor contains an amount equal to or less than about 1 pound of NOx per MWh of energy produced by the engine.

In a seventh aspect, provided herein is a method comprising the step of decreasing NOx emissions in a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the engine exhaust is operatively connected to the reactor and the operable connection between the engine exhaust and the reactor contains an injection inlet for the introduction of a reactive chemical agent to contact the engine exhaust prior to entrance of the engine exhaust into the reactor.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

THE FIGURE is a schematic illustration of one non-limiting embodiments of the methods, devices and systems provided herein demonstrating NOx removal for biogas engines placed at an anaerobic digestion facility placed at a concentrated animal feeding operation such as a dairy farm or other waste processing facility such as a waste water treatment plant. The anaerobic digester (1) is provided. In some embodiments, provided is reactor tank (2) attached to an anaerobic digester (1) and engine (e.g., a cogeneration unit, internal combustion engine, or biogas engine (3)). The reactor (2) utilizes urea and other endogenous reducing agents of the liquid waste stream (4) to decrease NOx emissions from the cogeneration unit (3). FIG. 1 depicts a reactor filled with packing media to increase the surface area.

DETAILED DESCRIPTION

The embodiments of the subject matter provided herein provide diaries, biogas engine providers, anaerobic digester facilities, and other producers and contributors of harmful gases to the environment with technology to make efforts to meet or exceed air quality regulations. An advantage of the subject matter provided herein is the use of spent liquid waste from the on-site anaerobic digester to cheaply scrub NOx from an engine or cogeneration unit's exhaust stream. Liquid/vapor NOx extraction and subsequent chemical conversion processes is enhanced by the unique liquid/vapor continuous-flow design of the subject matter provided herein which ensures a large excess of chemical reductant and limited contact time to enhance NOx removal while minimizing unwanted reverse reaction due to by-product saturation.

A feature of the subject matter provided herein is a reactor that is operatively connected to: (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit. As used herein, “biogas stream” comprises at least 50% methane. As used herein, “NOx” means oxides of nitrogen including as non-limiting examples NO, NO₂, and N₂O₅. As used herein, “COx” means oxides of carbon. As used herein, “SOx” means oxides of sulfur.

In certain embodiments, a reactor decreases SOx, NOx, and/or COx emissions from engine exhaust by contacting the engine exhaust with a liquid waste stream.

In further or additional embodiments, provided is a biogas production unit for converting waste to a biogas stream is an anaerobic digester. In some embodiments, provided is an anaerobic digester wherein the waste is agricultural waste. In some embodiments, the agricultural waste comprises feces or urine. In further or additional embodiments, the waste is municipal waste. In still further embodiments, the municipal waste comprises wastewater. In some embodiments, described herein is a system wherein the biogas production unit is a landfill. In further or additional embodiments, a waste stream is piped into a reactor from or at a landfill.

Biogas Production Unit

Another feature of the subject matter provided herein is a biogas production unit that is adapted to produce energy and an engine exhaust, and is operatively connected to a reactor that decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit. For example, in certain embodiments, the biogas production unit is an anaerobic digester. Anaerobic digesters are commercially available from the following sources: Accent Manufacturing, Inc.; Advanced Green Energy Solutions LLC; Acterra Group, Inc.; ADI Systems Inc.; American Anaerobic Digestion; Andgar Corporation; Applied Technologies, Inc.; BioEnergy Solutions; BIOFerm Energy Systems; Biogas Energy Inc.; Bioprocess Control AB; Boerger LLC; CCI BioEnergy Inc.; CH Four Biogas, Inc.; EcoCorp; Ecovation, Inc.; Energies Direct LLC; Entec Biogas USA/Reynolds Inc.; Environmental Credit Corp. (ECC); Environmental Fabrics, Inc.; Environmental Power/Microgy; Environmental Products & Technologies Corporation; Firestone Specialty Products; Gen-Tec LLC; GHD, Inc.; Groth Corporation; Industrial Telemetry Inc.; Integrys Energy Services, Inc.; NewBio E Systems, Inc.; Onsite Power Systems; Organic Waste Systems nv (OWS); Patz Corporation; Phase 3 Renewables; RCM International; ROS ROCA Envirotec; Schmack BioEnergy; Vaughan Company, Inc.; WesTech Engineering, Inc.; and Williams Engineering Associates.

Waste from a Biogas Production Unit

An additional feature of the subject matter provided herein is a biogas production unit including but not limited to an anaerobic digester that is adapted to convert a waste to a biogas stream. In certain embodiments, the waste is agricultural waste. In further or additional embodiments, the agricultural waste comprises feces or urine. In some embodiments, the animal waste is manure. Most animal manure is feces. Common forms of animal manure include farmyard manure (FYM) or farm slurry (liquid manure). FYM also contains plant material (often straw), which has been used as bedding for animals and has absorbed the feces and urine. Agricultural manure in liquid form, known as slurry, is produced by more intensive livestock rearing systems where concrete or slats are used, instead of straw bedding. Manure from different animals may have different qualities and require different application rates, such as manure from farm animals such as horses, cattle, pigs or sheep, chicken and turkey manures, rabbit manure, human sewage and guano from seabirds and bats. For instance, sheep manure is high in nitrogen and potash, and pig manure is relatively low in both. Horse manure also contains lots of weed seeds, as horses do not digest seeds the way that cattle do. Chicken manure, even when well rotted, is very concentrated and should be used sparingly.

In some embodiments, the waste is municipal waste. Municipal waste results at least in part from anthropogenic effects, processes or materials that are derived at least in part from human activities. In certain embodiments, the municipal waste comprises wastewater. Wastewater comprises any water that has been adversely affected in quality by anthropogenic influence. In certain embodiments, wastewater comprises liquid waste discharged by domestic residences, commercial properties, industry, and/or agriculture and can encompass a wide range of potential contaminants and concentrations. In the most common usage, it refers to the municipal wastewater that contains a broad spectrum of contaminants resulting from the mixing of wastewaters from different sources. In further or additional embodiments, the waste is sewage. Sewage is a subset of wastewater that is contaminated with feces or urine. As used herein, “sewage” includes domestic, municipal, or industrial liquid waste products disposed of, usually via a pipe or sewer or similar structure including for example a cesspool emptier. In still further or additional embodiments, the waste comprises an organic material, including for example waste from food processing facilities, paper mills, meat processing facilities, and the like.

Waste from a Landfill

An additional feature of the subject matter provided herein is a biogas production unit including but not limited to an anaerobic digester that is adapted to convert a waste to a biogas stream. In certain embodiments, the waste is from a biogas production unit that is a landfill. In specific embodiments, the waste from a landfill comprises a liquid waste. In further or additional embodiments, the landfill waste is piped into the systems described herein from the landfill.

Levels of Emissions from Reactor

Another feature of the subject matter provided herein are systems, methods and devices that are compliant with local, state and federal regulations that have established maximum levels of NOx, SOx, and/or COx emission limitations on emissions for biogas engines. In some embodiments, the methods, devices and systems provided herein are compliant with the NOx emission levels required by the California Energy Commission (CEC) guidelines for certification of combined heat and power engine systems established pursuant to California's recently enacted Waste, Heat and Carbon Emissions Reduction Act as of Sep. 1, 2010. In further or additional embodiments, the methods and devices and systems provided herein provide a decrease in emission levels over the conventional methods, devices, and/or systems, but are not compliant with the California Energy Commission (CEC) guidelines for certification of combined heat and power engine systems established pursuant to California's recently enacted Waste, Heat and Carbon Emissions Reduction Act as of Sep. 1, 2010

In some embodiments, provided herein are systems, methods and devices comprising a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit wherein the engine exhaust is operatively connected to the reactor and exhaust from the reactor contains an amount equal to or less than about 1 pound of NOx per MWh of electrical energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr).

In further or additional embodiments, provided herein are systems, methods and devices comprising a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit wherein exhaust from the reactor contains an amount equal to or less than about 0.9 pounds of NOx per MWh of electrical energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.75 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.5 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.4 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.3 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.2 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.1 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.07 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.05 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.03 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr), or exhaust from the reactor contains an amount equal to or less than about 0.01 pounds of NOx per MWh of energy produced by the engine crediting mechanical energy produced at the rate of 1 MWh per 1,341 horsepower-hour (hp-hr).

In further or additional embodiments, the methods and devices and systems provided herein are compliant with the NOx emission levels of Rule 4702 of the San Joaquin Air Board established as of Sep. 1, 2010. The San Joaquin Air Board determines the NOx emission level by: (1) measuring NOx concentration in the exhaust; and (2) measuring the oxygen concentration in the exhaust. To correct for the differences in the oxygen level for two kinds of engines (rich v. lean burn engines), the Board adjusts proportionately both the NOx and the oxygen concentration so that the oxygen level in the exhaust equals 15%. For example, if the exhaust from an engine has 5 ppm NOx and 10% oxygen concentration, an adjustment of the oxygen concentration to 15% and the NOx level to 7.5 ppm is necessary. Thus, as used herein, the “San Joaquin Air Board Level” takes into account this adjustment in NOx level relative to oxygen concentration such that the oxygen level in the exhaust equals 15%.

In some embodiments, provided herein are systems, methods and devices comprising a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit and exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.4 grams of NOx per horsepower-hour of electrical energy produced by the engine.

In further or additional embodiments, the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.35 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.3 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.25 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.2 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.15 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.1 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.05 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.03 grams of NOx per horsepower-hour of electrical energy produced by the engine, or the exhaust from the reactor contains a San Joaquin Air Board Level equal to or less than about 0.01 grams of NOx per horsepower-hour of electrical energy produced by the engine.

Engines

Another feature of the subject matter provided herein is an engine that utilizes a biogas stream from a biogas producing unit to produce energy and an engine exhaust; wherein a reactor decreases NOx emissions from the engine exhaust by contacting the engine exhaust with a liquid waste stream provided from the biogas production unit. In some embodiments, the engine is an internal combustion engine, cogeneration unit, or turbine. In further or additional embodiments, the internal combustion comprises at least one biogas engine. In some embodiments, provided are at least two biogas engines. In some embodiments, the engine is a cogeneration unit or turbine.

Biogas engines are commercially available from the following sources: Acterra Group, Inc.; Advanced Green Energy Solutions LLC; Capstone Turbine Corporation; Caterpillar Electric Power; Charles Equipment Company; Cummins Engines; Dresser Waukesha; Guascor; PRO2; FABCO Power Systems; GE Jenbacher Gas Engines; Gen-Tec LLC; Ingersoll Rand Energy Systems; Inland Power Group; Kraft Power Corporation; MAN Engines & Components Inc.; Martin Machinery; Stewart Engineered Equipment Company, Inc.; and Unison Solutions, Inc.

Injection of Fluid into Engine Exhaust

Another feature of the subject matter described herein is a method, device and system comprising an engine that is operatively connected to a reactor and the operable connection between the engine and the reactor contains an injection inlet for the introduction of a reactive chemical agent to contact the engine exhaust prior to entrance of the engine exhaust into the reactor. In further or additional embodiments, the reactive chemical agent comprises urea, ammonia, water, or air. For example, in certain embodiments, the injection of fluid is a pretreatment of the engine exhaust and the injection site is at the operable connection between the engine and the reactor (5) of FIG. 1. In some embodiments, the reactive chemical agent comprises urea, ammonia, water, or air. In a specific embodiment, provided is a method comprising the step of decreasing NOx emissions in a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust; wherein the engine exhaust is operatively connected to the reactor and the operable connection between the engine exhaust and the reactor contains an injection inlet for the introduction of a reactive chemical agent to contact the engine exhaust prior to entrance of the engine exhaust into the reactor.

Reactors

Yet another feature of the subject matter provided herein is a method, device and system comprising an a reactor that is operatively connected to (a) a biogas production unit for converting waste to a biogas stream; and (b) an engine that utilizes the biogas stream from the biogas producing unit to produce energy and an engine exhaust. The reactor of the methods, devices and systems provided herein facilitates the attenuation of NOx emission from biogas combustion utilizing a liquid waste stream utilizing principles of extended absorption, wet chemical scrubbing, and/or selective non-catalytic reduction. In certain embodiments, the reactor comprises packing media to increase the surface area for the removal of NOx, COx, and SOx from engine exhaust.

Agents Used in the Reactor

Provided herein, in certain embodiments, is a reactor comprising at least one reactive chemical agent that is provided from a liquid waste stream from a biogas production unit. The reactive chemical agent is utilized to decrease the levels of NOx, COx, and/or SOx from engine exhaust. In certain embodiments, the reactive chemical agent is a nitrogen-containing organic compound. For example, in some embodiments, the nitrogen-containing organic compound is urea or ammonia. In further or additional embodiments, the reactive chemical agent comprises an oxidizing or reducing agent.

In some embodiments, the reactive chemical agent comprises a reducing agent. In certain embodiments, the reducing agent comprises urea or ammonia. In further or additional embodiments, the reactive chemical agent comprises an oxidizing agent. In some embodiments, the oxidizing agent is oxygen. For example, in certain embodiments, the oxygen is provided from an engine or is exogenous and is provided from a source outside of the system (e.g. air). In further embodiments, the reactive chemical agent comprises urea, ammonia, water, or air. In additional embodiments, at least one reactive chemical agent is provided from a biogas production unit. In yet further embodiments, all of the reactive chemical agents are provided from the biogas production unit. Further, in certain situations, heat from the cogeneration unit (or biogas engine or turbine) is used to augment and/or enhance the chemical reactions occurring in the reactor.

In still further embodiments, the reactive chemical agent comprises a nitrogen-containing compound or a salt thereof. For example, in specific embodiments, the reactive chemical agent comprises isocyanuric acid, a hydroxylamine, hydrazine, or cyanuric acid. In further or additional embodiments, the reactive chemical agent comprises an ammonium salt. In specific embodiments, the ammonium salt is ammonium carbamate, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, ammonium malate, or ammonium maleate.

Extended Absorption

In a specific embodiment of the subject matter described herein, provided is a method, device and system utilizing a reactor that decreases NOx levels using extended absorption. The process of extended absorption to decrease NOx levels of engine exhaust as utilized in the present disclosure proceeds as follows. The biogas engine burns the biogas to produce an exhaust comprising COx, NOx, and/or SOx.

Hot nitric oxide (NO) is then cooled to approximately 100° F. (38° C.) where it reacts non-catalytically and exothermically with oxygen to form nitrogen dioxide (Equation 1). The cooler temperatures are necessary to prevent the reverse reaction and ensure maximum production of NO₂. The final step for producing nitric acid involves absorption of NO₂ into water where it reacts to form nitric acid.

The rate of this final reaction is controlled by three important steps: (1) the non-catalytic, gas phase oxidation of NO to NO₂, (2) diffusion of the NO₂ from the gas phase into the liquid phase, and (3) exothermic chemical reaction with water in the liquid phase (Equation 2). This final step regenerates an equivalent of NO which must either be oxidized to NO₂ and absorbed into water or emitted from the engine as waste. If not captured within the absorption tower, NOx exits the plant as part of the absorber tail gas emissions. In certain embodiments, NOx is a valuable product as it is readily converted to a desired commercial chemical, nitric acid.

As shown in Equation 3 one mole of NO is formed for every three moles of NO₂ absorbed: 2NO+O₂→2NO₂+heat  Equation 1 3NO₂+H₂O→2HNO₃+NO+heat  Equation 2

Vent gas containing NOx is released to the atmosphere from the reactor only after the gas becomes too dilute to recycle further. Thus, the process of extended absorption as implemented in the present disclosure is utilized in the reactor to remove NOx from the biogas exhaust. In some embodiments, provided is a reactor comprising an absorption chamber that reduces NOx emissions from the engine exhaust using extended absorption.

Yet another feature of the subject matter provided herein is the optimization of an extended absorption process. The four most important factors influencing the efficiency of the extended absorption process provided herein is: (1) temperature, (2) pressure within the absorption chamber (e.g., the reactor), (3) acidity of the absorbing solution, and (4) retention time within the absorption chamber (e.g., reactor).

First, temperature is a parameter in NOx absorption efficiency. Excess heat comes into the system from two sources: the high ambient temperature of the emissions stream and the absorption and subsequent chemical reaction of NOx in the absorbing liquid to form nitric acid. Both the absorption and the reaction are exothermic and release approximately 135 kJ/mole². In some embodiments, provided is a reactor wherein the average temperature within the reactor is within the range of about 50° C. to about 0° C. Without being limited by theory, it is believed that temperature ranges within about 50° C. to about 0° C. will provide optimum conditions for extended absorption resulting in more efficient transfer of NOx from the gas to solution phase. In further or additional embodiments, the average temperature within the reactor is equal to or less than about 50° C., is equal to or less than about 45° C., is equal to or less than about 38° C., is equal to or less than about 35° C., is equal to or less than about 30° C., is equal to or less than about 25° C., is equal to or less than about 20° C., or is equal to or less than about 10° C.

Second, pressure within the absorption chamber is a parameter in NOx absorption efficiency. Without being limited by theory, it is believed that the rate of oxidation of NO and the rate of absorption of NO₂ into solution is impacted by pressure because the uncatalyzed air oxidation of NO typically requires minutes, whereas absorption of NO₂ is complete within seconds. Thus the oxidation of NO is rate limiting, so additional absorption tower pressure, which in certain embodiments is in the form of compressed air, has its largest impact on overall absorption efficiency through increasing the rate of NO oxidation. In some embodiments, the average pressure within the absorption chamber is maintained in the range of about 1 atm to about 15 atm. In further or additional embodiments, the average pressure within the absorption chamber is within about 4 atm to about 12 atm, or is within about 10 atm to about 6 atm, or is about 8 atm.

Third, acidity of the absorbing solution is a parameter in NOx absorption efficiency. Without being limited by theory, it is believed that more basic conditions are preferred in order to facilitate the dissolution of acidic NOx into solution. In some embodiments, the average pH of the absorbing solution within the reactor is within the range of about 5.5 to about 9. In further or additional embodiments, the pH of the absorbing solution within the reactor is within the range of about 6 to about 8.5, or within about 6.5 to about 8, or is about 7, or is about 8, or is about 8.5, or is about 9, or is about 9.5.

Fourth, retention time within the absorption chamber is a parameter in NOx absorption efficiency.

“Retention time” is the period of time a gas sample is maintained in the reactor. Without being limited by theory, it is believed that a longer retention time will result in an increase in the transfer of NOx from the gas to solution phase. Retention time is measured in minutes by dividing the volume of the reactor (in liters) by the flow of gaseous NOx (in liters/minute). In some embodiments, provided is a reactor that has a retention time of NOx within the range of at least about 1 second to at least about 15 seconds. In some embodiments, the retention time is at least about 1 second, at least about 2 seconds, at least about 3 seconds, at least about 4 seconds, at least about 5 seconds, at least about 6 seconds, at least about 7 seconds, at least about 8 seconds, at least about 10 seconds, at least about 12 seconds, at least about 15 seconds, or at least about 20 seconds.

Wet Chemical Scrubbing

In a specific embodiment of the subject matter described herein, provided is a method, device and system utilizing a reactor that decreases NOx levels using wet chemical scrubbing. Provided herein are two techniques utilizing acid-base chemistry to decrease NOx emissions from an engine. The processes described herein use either ammonia or urea to “scrub” NOx from engine tail gas streams through conversion to either nitrates or nitrites.

Ammonia-Based Scrubbing

In one embodiment, the reactor utilizes ammonia from a liquid waste stream provided from a biogas production unit to scrub and therefore decrease NOx emissions from an engine. The process proceeds in the following manner to produce ammonium nitrate (Equation 3). NOx+H₂O→HNO₃ HNO₃+NH₃→NH₄NO₃(ammonium nitrate)  Equation 3

In certain situations, ammonium nitrite is formed then oxidized to ammonium nitrate. For example, a combination of high dilution and air/photo-oxidation provides the necessary oxidization conditions, as dilute aqueous solutions of ammonium nitrite are oxidized to ammonium nitrate within about 24 hours at room temperature (Equation 4). NO+NH₃→HNO₂ HNO₂+NH₃→NH₄NO₂(ammonium nitrite) NH₄NO₂+O₂→NH₄NO₃  Equation 4

Urea-Based Scrubbing

In one embodiment, the reactor utilizes urea ((H₂N)₂CO) from a liquid waste stream provided from a biogas production unit to scrub and therefore decrease NOx emissions from an engine. This method involves selective non-catalytic reduction (SNCR) of NOx as depicted in the reactions of Equation 5. HNO₂+(H₂N)₂CO→HNCO+N₂+H₂O HNCO+HNO₂→N₂+CO₂+H₂O HNCO+H₂O→NH₃+CO₂ HNO₃+NH₃→NH₄NO₃  Equation 5

In further or additional embodiments, urea can also facilitate the SNCR of nitric acid through the mechanism depicted in Equation 6. 6HNO₃+5(H₂N)₂CO→8N₂+5CO₂+13H₂O  Equation 6

In still further or additional embodiments, dissolved ammonia, in the form of ammonium hydroxide, within the liquid waste stream participates in SNCR of both nitric and nitrous acid as shown in Equation 7. As shown below, three moles of nitric acid are reduced by five moles of ammonium hydroxide, whereas only one mole of ammonium hydroxide is required to reduce one mole of nitrous acid. 3HNO₃+5NH₄OH→4N₂+14H₂O HNO₂+NH₄OH→N₂+H₂O  Equation 7

While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. The methods, devices, and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions and changes in the form of the formulations, methods, and systems described herein may be made without departing from the spirit of this disclosure. The accompanying claims and their equivalents are intended to cover such forms or modifications.

EXAMPLES

The following specific examples are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

In the following examples, the NOx emissions are analyzed at points before and after scrubbing. The measurement of NOx is determined using a portable combustion gas analyzer. Suitable instruments are available through Clean Air Equipment Rental. These instruments (ie, Model ECOM AC+ or Testo 350XL) can measure O₂, CO, CO₂, NO, NO₂, and SO₂ with 2% accuracy over a range from several thousand ppm down to less than 10 ppm. They are designed for either high (up to 1600° F.) or low (30° F.) temperature use in the measurement of boiler flue gas, engine emissions, and the environmental reporting of stack gas parameters.

NOx will be generated by a small internal combustion engine and piped directly into the bottom of the absorption tower. The amount of NOx leaving the engine within the exhaust stream is measured and recorded at the beginning and end of each experiment. Both the length and configuration of the pipe leading to the absorption tower are used to cool the emissions to below 100° F. The exhaust is allowed to fill the absorption tower and exit the top via a stack. Measurements of NOx concentration is obtained and recorded on these emissions as they exit the stack.

Representative liquid waste for use in experimentation will be obtained from the Van Ommering Dairy (Lakeside, Calif.), Bull Frog Dairy (El Centro, Calif.), or the Fiscalini Cheese Company (Modesto, Calif.). The bulk of the waste will be stored, when not in use, in a sealed vessel under refrigeration. For experiments, liquid waste is circulated from a measured aliquot within a flask or beaker via electric pump to the top of the absorption tower were it will be pumped into the first chamber and allowed to drain by gravity throughout the entire length of the absorption tower. The liquid will exit the bottom of the absorption tower through a valve and is funneled back into either a separate flask or the original holding flask. In this way a determination is made as to the necessity for either “fresh” or re-circulated digester waste as it relates to the degree of NOx removed via the absorption tower.

Example 1 Optimization of the Scrubbing Apparatus Configuration: Temperature and Pressure within the Absorption Tower

The temperature within the absorption tower is kept below 38° C. or 100° F. to ensure efficient absorption of NOx. The high ambient temperature of the biogas exhaust emissions stream can be maintained by piping the exhaust to the absorption tower. The optimal distance between the cogeneration unit and the absorption tower is determined by measuring exhaust temperature as a function of distance from the engine.

The heat generated by the absorption of NO₂ into water and subsequent reaction with water to yield nitric acid (exothermic, 135 kJ/mole²) is dissipated through the relatively large volume of waste stream water being cycled through the absorption tower. Furthermore the anaerobic digester liquid waste stream will not exceed 100° F. The added cost associated with installation and maintenance of refrigeration equipment should, therefore, be avoided.

Example 2 Optimization of the Scrubbing Apparatus Configuration: pH of the Absorbing Liquid within the Absorption Tower

The optimum operating range for anaerobic digestion is pH 6.8 to 8.5. This is well above the range where NO₂ absorption begins to slow down (50% HNO₃ where the pH is effectively zero). Furthermore, due to the constant flow design of most anaerobic digesters, “fresh” aqueous waste will be cycling through the absorption tower during all periods of operation. Thus the rate of NO₂ absorption as a function of water pH should remain constant and high.

Example 3 Optimization of the Scrubbing Apparatus Configuration: Retention Time of the Emissions within the Absorption Tower

In order to obtain sufficiently long retention times a number of absorption chambers are combined in series. The number and size of these chambers is determined by the volume of emissions generated per unit time. As a rough approximation, the volume of the emissions should be equal to the volume of biogas burned plus the volume of air mixed into the gas at the time of combustion. The temperature of the emissions will greatly expand the volume of the emissions, so this approximation is only true after the emissions have cooled.

The examples and embodiments described herein are for illustrative purposes only and various modifications or changes are included within the spirit and purview of this application and scope of the appended claims. 

1. A system comprising a reactor comprising a liquid waste stream inlet and an engine exhaust inlet, the reactor operatively connected to: (a) a biogas production unit constructed so as to convert waste to a biogas stream and a liquid waste stream and comprising a biogas stream outlet and a liquid waste stream outlet connected to the liquid waste stream inlet of the reactor; and (b) an internal combustion engine constructed so as to utilize the biogas stream to produce energy and an engine exhaust including NOx and comprising a biogas stream inlet connected to the biogas stream outlet of the biogas production unit and an engine exhaust outlet connected to the engine exhaust inlet of the reactor; wherein the reactor is constructed so as to generate a treated exhaust with decreased NOx emissions by contacting the engine exhaust with the liquid waste stream from the biogas production unit.
 2. The system of claim 1 wherein the biogas production unit for converting waste to a biogas stream is an anaerobic digester.
 3. The anaerobic digester of claim 2 wherein the waste is agricultural waste.
 4. The anaerobic digester of claim 2 wherein the waste is municipal waste.
 5. The anaerobic digester of claim 4 wherein the municipal waste comprises wastewater.
 6. The system of claim 1 wherein the treated exhaust contains a San Joaquin Air Board Level equal to or less than about 0.4 grams of NOx per horsepower-hour of energy produced by the engine.
 7. The system of claim 1 wherein the treated exhaust contains a San Joaquin Air Board Level equal to or less than about 0.1 grams of NOx per horsepower-hour of energy produced by the engine.
 8. The system of claim 1 wherein the engine exhaust includes SOx and the treated exhaust has decreased SOx emissions.
 9. The system of claim 1 wherein the engine exhaust includes COx and the treated exhaust has decreased COx emissions.
 10. The system of claim 1 wherein either the engine exhaust outlet or the engine exhaust inlet includes an injection inlet for the introduction of a reactive chemical agent to contact the engine exhaust prior to entrance of the engine exhaust into the reactor.
 11. A reactor comprising a liquid waste stream inlet and an engine exhaust inlet, the reactor operatively connected to: (a) a biogas production unit constructed so as to convert stream waste to a biogas stream and a liquid waste stream and comprising a biogas stream outlet and a liquid waste stream outlet connected to the liquid waste stream inlet of the reactor; and (b) an internal combustion engine constructed so as to utilize the biogas stream to produce energy and an engine exhaust including NOx and comprising a biogas stream inlet connected to the biogas stream out et of the biogas production unit and an engine exhaust outlet connected to the engine exhaust inlet of the reactor; wherein the reactor is constructed so as to generate a treated exhaust which contains an amount equal to or less than about 1 pound of NOx per MWh of energy produced by the engine by contacting the engine exhaust with the liquid waste stream from the biogas production unit.
 12. The reactor of claim 11 wherein the treated exhaust contains an amount equal to or less than about 0.75 pounds of NOx per MWh of energy produced by the engine.
 13. The reactor of claim 11 wherein the treated exhaust contains an amount equal to or less than about 0.1 pounds of NOx per MWh of energy produced by the engine.
 14. The reactor of claim 11 wherein the reactor includes an absorption chamber to reduce NOx emissions from the engine exhaust using extended absorption.
 15. The reactor of claim 14 wherein the reactor is capable of maintaining a temperature within the reactor within the range of about 50° C. to about 0° C.
 16. The reactor of claim 14 wherein the reactor is capable of maintaining a pressure within the reactor within the range of about 1 atm to about 15 atm.
 17. The reactor of claim 14 wherein the reactor is capable of maintaining the pH of an absorbing solution within the reactor within the range of about 5.5 to about
 9. 18. The reactor of claim 14 wherein the absorption chamber is constructed such that the retention time of NOx is within the range of about 1 second to about 20 seconds.
 19. A method of decreasing NOx emissions in an engine exhaust comprising: i) providing the system of claim 1; and ii) contacting the engine exhaust from the internal combustion engine with the liquid waste stream from the biogas production unit to generate a treated exhaust with decreased NOx emissions. 